Chlorinated amines from chlorinated hydroaromatic ketimino compounds and process of making same



' Patented Apr. 24,1928.

UNITED STATES PATENT OFFICEtf 'lflODOB-E vomz, or nasnn, swrrznnmmn, assrenon are new a nvemurnl s. a, or nasnn'swrrznnnann.

CHLOBINATED AIINES FROM CHLORINATED HYDROAROHATIG KETII INO COI- POUNDS AND PROCESS OF MAKING SAME. i

No Drawing. Application filed May 21, 1923, Serial No. 640,554, and in Germany June 3, 1828 In a previous application for Letters Patent Serial No. 621,095, filed Febraury 24;,

1923, there are described highly chlorinated hydro-aromatic products containing nitrogen. W

According to the present invention these bodies can be reduced and the reaction can be so conducted that all the nitrogen remains in the molecule so that chlorinated amines are produced. It is essential that hydrolysis should be avoided as much as possible. Since, however, the 'chloroketimines of the said applicationare relatively stable bodies which only when standing with mineral acids or when boiled with such acids are transformed into the corresponding ketones, the reduction produces good yields of amine even when conducted in presence of acids provided that the reduction takes place 20. rapidly. The final product of the reduction depends onthe reducing agent which has beenused'. Strong reducing agents such as zinc and hydrochloric acid have a greater tendency to remove chlorine atoms than feeble'reduc'ing agents. Among such feeble agents a solution of calcined sodium sulfide I in ethyl ormethyl alcohol has been observed to act.-- particularly well; where this agent is still too strong,'-alcohol alonecan be used. The chlorinated amines, which are obtained in good yield are partly new bodies, such as for instance 7 2: 3: 4-trichloro-1- phthylamine which melts at 162? (l.- 1: ichloro-2- naphthylamine, which melts at 93.5 C.

- N-Ol minohexahydroben'zene,

3. 250 grams of calcined'sodium sulfide are dissolved in 1m 1m! and a nation a chloro-l-amino-anthraquinone, which melts at 204 C.

1n the case of the known compounds the pure form and in a short time from cheap' parent materials. 2: 3: 4: (i-tetrachloraniline. 'Also 4-trichloro-2-naphthylamine described by Claus (Journal fiir Praktische Ghemie, vol.

57 page 1) is obtained advantageously according to the invention.

The following examples illustrate the invention: I

1. Hexachloro chloroketiminotetrahydrobenzene, the exact constitution whereof is 2: 2 t 3 1 4: 6-hexachloro-l-chloroketimino- 1:2:3:4-tetrahydrobenzene, is dissolved in The same -ap lies to e 1:31

methyl alcohol and the solution is'run into tallized from light petroleum. The reaction m the example takes place according to the following formula:

scribed in Example 1. .Pentachloraniline is obtained with a 'eld of about per cent.v The reactionin t exam letakes place-according to the-following ormula:

' left in the solution.

filtered and cooled down. A quantity of sodium, sulfide crystallizes and the same is The latter is maintained at a temperature of 30 0., while 200 grams of pentachloro-2-chloroketiminotetrahydronaphthalene, the exact constitution of which is 1: 1: 3: 3: 4-pentachloro-2-chlorokietimino 1: 2:3 4.- tetrahydronaphthalene, are introduced in small portions. When they reaction is complete the mixture is again reducing agent) 4. The l-chloroketimino derivative is substituted for the 2-derivative in Example 3. In this case 2:3z-trichloro-l-naphthyl- N-Ol reducing agent) 5. Pentachloro 2 cliloroketiminotetrahydronaphthalene; the exact constitution whereof is 1: 1: 3: 3 4-oentachloro-2-chloro- -ketimino-1 2: 3 :'4-tet'rahydronaphthalene, is

dissolved in methyl alcohol and hydrochloric acidand-zinc dust are added alternately in small portions to the solution. When the reaction is complete the mixture is filtered and water-is added to the filtrate, wherebyreducing agent) 6. Pentachloro 1 chloroketiminotetrahydroanthraquinone, the exact constitution of which is 2: 2: 3 4: 4 pentachloro-l-chloroketimino-l :2: 3 4: tetrahydroanthraqu'inone, is boiled in alcohol for several hours 0 N.Gl

reeul ieduci il agent) The Hroduct obtained is a brickred crystalline pow er which is soluble in hot glacial acetic acid and melts at 240 C. v

7. Pentachloro 1 chloroketiminotetrahy- (resulting from the (resulting from the (resulting Item the lromthe newness heated on the water-bath. The solution is now mixed with Water, whereby the amine is precipitated and any naphthol which may have been formed remains in the solution.

The precipitate is dried and recrystallized from benzene. The yield is about 90 per cent of pure 1 :3 :4 trichloro 2 naphthylamine. The reaction in this example takes place accordingvto the following formula:

amine in good yield is obtained according to' the following formula:

the amine containing some naphthol is precipitated. The naphthol may be removed by means of sodium carbonate. The dried amine is recrystallized from methyl alcohol. The yield of dichloro-2-naphthylamine amounts to about 78 per cent of that theoretically possible. The reaction in this example takias place according to the following formu a:

NB, i inoi' on the reflow pooler. A good yield of 2: 3: 4- trichloro- 1 aminoanthraquinone in pure form is obtained according to the following formula:

roketimino-l 2 3 4 tetrahydroanthraquinone, is introduced in small portions into a solution of stannous chloride and of hydrogen chloride dissolved in methyl alcohol. When the reaction is complete the mixtureis brought to a boil, the amine precipitated by droxyl derivative by treatment with a sodium carbonate solution. The dichloro-laniinoanthraquinone is recrystallized from benzene. Thereaction in this example takes addition of. water and purified from by place according to the following formula:

0 N.Ol E NH.

-o n moi H ulti fro the 0 4 Ol ifiudn i agaii 0 01 A c1 1 a What I claim is: a a

1. A process for the manufacture of chlorinated aromatic amines, consisting in treating a hydroaromatic benzene derivative containing nitrogen in the form of a chlorinated ketimino group and having in the same hydroaromatic nucleus most of the hydrogen atoms substituted by chlorine, with a reducing agent at a moderate temperature and so far as possible with exclusion of water'and strong acids. i I

2. A process for the manufacture of chlorinated aromatic amines, consisting in treatinga hydroaromatic benzene derivative containing nitrogen in the form of a chlorinated ketimino group and having in the same hy- Y droaromatic nucleus most of thehydrogen atoms substituted by chlorine, with a feeble reducing agent at a moderate temperature and so far as possible with exclusion of water and strong acids. I

3. A process for the manufacture of chlo-.

rinated aromatic amines, consisting in treating' a hydroaroinatic benzene derivative containing nitrogen in the form of a chlorinated ketimino group and having inthe same hymy name this 8th droaromatic nucleus most of the hydro en atoms substituted by chlorine, with an a oholic sulphide solution at a moderate temperature and so far as possible with exclusion of water and strongacids.

4. A process for the manufacture of 2: 3 4-trichloro-l-aminoanthraquinone, consisting in treating 2:2:3:4:4-pentachloro- 1 chloroketimino 1 2: 3': 4 tetrahydroan thraquinone with a feebleireducing agent at ,amoderate temperature and so far as possible with exclusion of water and strong acids. 7

5. As a new article of manufacture the hereinbefore described 2:3:4-trichloro- 1- aminothraquinone obtained by treating 2 :2 3 4 4- pentachloro 1 chloroketimino- -1:2:3: 4-tetrahyroanthraquinone with a feeble reducing agent at a moderate temperature and so far as possible with exclusion ofwater and strong acids, said body forming a brick red cristalline powder soluble in hot glacial acetic acid andmelt-ing at 240 C.

In witness whereof I have hereunto signed day of May 1923.

THEODORE VOLTZ. 

